Polymerizable compositions containing olefin metathesis catalysts and cocatalysts, and methods of use therefor

ABSTRACT

Polymerization of ring-strained cyclic olefins takes place in the presence of a one-part or two-part catalyst which is air and moisture stable and which comprises a transition metal-containing compound. 
     The one-part transition metal-containing catalyst is selected from the group consisting of 
     (a) compounds of the formula 
     
         (L.sup.1) (L.sup.2)Q 
    
      wherein 
     Q represents Mo or W; 
     L 1  represents one to six CO (carbonyl) ligands; 
     L 2  represents none to 5 ligands, each of which is a non-ionic compound or unit of a polymer which can be the same or different, each contributes two, four, or six electrons to the metal and is different from L 1  ; 
     wherein the sum of the valence electrons of Q and the electrons contributed by the ligands L 1  and L 2  is 18, 
     (b) at least one of cationic ruthenium and osmium-containing organometallic salts having at least one polyene ligand, and 
     (c) [Ir(RO 2  CHC=CHCO 2  R) 2  Cl] 2  wherein each R independently is hydrogen or lower alkyl (C 1  to C 4 ), provided that the oxidation state of the metal is in the range of +3 to 0, and that cocatalysts containing C-halogen bonds are not present. 
     The two-part catalyst comprises 
     (a) a transition metal-containing catalyst, provided that the oxidation state of the transition metal is in the range of +3 to 0, and 
     (b) a cocatalyst selected from the group consisting of 
     (i) terminal or silyl alkynes, 
     (ii) organosilanes containing at least ##STR1## (iii) oxidative salts or oxidative compounds containing an oxygen atom to non-oxygen atom double bond, and 
     (iv) heteroatom-containing alkenes. 
     The polymerized composition is useful to provide molded articles, elastomers, dielectric supports, ionophoric or biologically active materials, composite materials, and the like.

FIELD OF THE INVENTION

This invention relates to polymerization of ringstrained cyclic olefinsby means of a one-part or two-part catalyst which comprises a transitionmetal-containing compound. The polymerized composition is useful toprovide molded articles, elastomers, dielectric supports, ionophoric orbiologically active materials, and composite materials.

BACKGROUND OF THE INVENTION

It is known in the art that polymerization of cyclic olefins providesunsaturated polymers which were disclosed to be useful, for example, asmolded articles.

Polymerization of cyclic olefins via the so-called olefin metathesisreaction has been widely investigated since the first descriptionappeared in 1960. Ivin has reviewed the work in this field (K. J. Ivin,"Cycloalkenes and Bicycloalkenes," Chapter 3 in K. J. Ivin, T. Saegusa,eds. Ring-Opening Polymerization, Vol. 1, Elsevier: London, 1984,121-183). Polymers produced via olefin metathesis of cyclic olefinsstill contain ##STR2## bonds, one for each monomer unit, and are thusdistinct from polymers prepared using free radical or Ziegler-typecatalysts, which produce saturated hydrocarbon polymers, and polymersprepared using ring-opening polymerizations of cationically sensitivemonomers such as epoxides, in which heteroatoms are present and areinvolved in the polymerization chemistry by cleavage of aheteroatom-carbon bond.

As this review and many patents teach, certain transition metalcompounds can be used to catalyze olefin metathesis polymerization ofcyclic olefins. Molybdenum (Mo), tungsten (W), and rhenium (Re),incorporated in either inorganic or organometallic compounds, have mostoften been employed. Catalysts based on transition metals from PeriodicGroups 4, 5, 8, and 9 are also known. Heterogeneous catalysts have beentaught, typically supported on alumina or silica. Most useful, however,are homogeneous or non-supported catalysts. The most frequently usedhomogeneous catalysts are based on high oxidation state compounds of Moor W, such as WCl₆, WOCl₄ or MoCl₆. Reaction products of these withphenolic compounds are also taught Cocatalysts, usually containing analkyl group bonded to a non-transition metal, are often used incombination with these, and cocatalysts are presumed to transfer atleast one alkyl group to the transition metal. Most frequently, thecocatalysts are based on aluminum (Al), but alkyls of zinc, tin andother Group 14 metals, Group 1 metals (such as lithium), and Group 2metals (such as magnesium) are also employed. Cocatalysts which arehalogen-containing Lewis acids such as AlCl₃ or sources of halide,either organic, organometallic, or inorganic, may be used in combinationwith the transition metal-containing compound. Organic reagents may beadded to slow the rate of polymerization; typically these containLewis-basic groups, usually containing nitrogen or oxygen. Morespecialized catalysts, usually organometallic compounds, are also known,and the most widely used of these are based on W or titanium (Ti). As isappreciated by those skilled in the art, all of these systems aresensitive to water and air, some violently so, and accordingly the usualpractice is to remove adventitious amounts of water and air or belimited to processes and compounds in which materials free of theseimpurities can be supplied to the catalyst. A robust W organometalliccompound has recently been described (L. L. Blosch, K. Abbound, J. M.Boncella J. Amer. Chem. Soc. 1991, 113, 7066-7068), but it requires theuse of water-sensitive AlCl₃ as cocatalyst to be active as an olefinmetathesis polymerization catalyst. Certain of the above catalysts andcocatalysts may have other disadvantages as well. For example, use oforganic sources of halide such as CCl₄ is undesirable because suchcompounds are carcinogenic. Use of alkyltin compounds is undesirablebecause such materials are known to be toxic to certain organisms andharmful to humans, and they are heavily regulated by such agencies asthe U.S. Environmental Protection Agency, particularly with respect touse and disposal. Still other systems require the use of solvents,making them unsuitable for solvent-free processes; solvent-freeprocesses are desirable because they provide environmental and costadvantages.

A smaller body of background art teaches the use of Periodic Groups 8and 9 transition metal compounds for olefin metathesis, especiallycompounds containing ruthenium (Ru), osmium (Os), and iridium (Ir). U.S.Pat. Nos. 3,367,924 and 3,435,016 disclose use of Ir halides and R. E.Rinehart and H. P. Smith in J. Polym. Sci., B (Polymer Letters) 1965, 3,pp 1049-1052 disclose Ru halides as catalysts for olefin metathesispolymerization of cyclic olefins in inert and protic solvents, includingwater. F. W. Michelotti and W. P. Keaveney in J. Polym. Sci: A 1965, 3,pp 895-905 describe hydrated trichlorides of Ru, Ir and Os aspolymerization catalysts in alcohol solvents. F. W. Michelotti and J. H.Carter in Polymer Preprints 1965, 6, pp 224-233 describe the use ofIrCl₃ ·3H2O under nitrogen atmosphere to produce polymer in varyingyields from functional group-containing norbornenes. Grubbs in U.S. Pat.Nos. 4,883,851, 4,945,144, and 4,945,141 teach Ru and Os compounds ascatalysts for polymerization of 7-oxanorbornenes. It is believed thatcocatalysts have not been described for Ru, Os, or Ir-containing olefinmetathesis polymerization catalysts.

Certain olefin metathesis polymerization cocatalysts which are notsensitive to air or water have been taught; however, they are used incombination with air or water sensitive transition metal compounds, sothat the reaction mixture still must be scrubbed of, and protected fromwater or air or both. U.S. Pat. No. 4,490,512 and K. Weiss and R. Gollerin J. Mol. Catal. 1986, 36, 39-45 disclose ring-opening metathesis ofcycloolefins (e.g., cyclopentene or cycloheptene) in the presence ofWCl₆ and a 1-alkyne to give, for example, poly-1-pentenylene orpoly-1-heptenylene, respectively. U.S. Pat. No. 4,334,048 describes theuse of acetylenes with air-sensitive W-carbene compound under inertconditions to give low yields of polymer.

Cocatalysts containing silyl hydride ##STR3## are used with the reactionproducts obtained from air-sensitive tungsten halide plus a phenoliccompound as disclosed in U.S. Pat. No. 4,994,426 for polymerization ofsubstituted norbornenes. A combination of a tungsten compound and atin-hydride has also been employed in U.S. Pat. Nos. 5,019,544 and4,729,976. Z. Foltynowicz, B. Marciniec, and C. Pietraszuk in J. Mol.Catal. 1991, 65, 113-125 describe reaction of vinyltriethoxysilane asreagent with alkenes in the presence of RuCl₃ and RuCl₂ (PPh₃)₃ (whereinPh=phenyl), although they do not teach polymerization of cyclic olefins.

Oxidative cocatalysts have been used in various circumstances. Forexample, oxygen is described as having varying effects upon on olefinmetathesis polymerization catalysts by V. A. Bhanu and K. Kishore inChem. Rev. 1991, 91 (2), pp 99-117 (see especially 112-113). Inparticular, apparent beneficial effects of oxygen (O₂) uponRu-containing compound catalyzed norbornene polymerization reactions areattributed to initial epoxide formation by K. J. Ivin, B. S. R. Reddy,and J. J. Rooney in J. Chem. Soc., Chem. Comm. 1981, 1062-1064.

In non-analogous art, the effect of [Cp₂ Fe]⁺ PF₆ ⁻ on W-containingcatalysts for alkyne polymerization has been described by M.-H. Desboisand D. Astruc in New J. Chem. 1989, 13, 595-600. Photoassisted W(CO)₆catalysts for acetylene polymerization have been disclosed by S. J.Landon, P. M. Shulman and G. L. Geoffroy, in J. Am. Chem. Soc. 1985 107,6739-6740.

Heteroatom-containing alkene reagents have been disclosed by C. T. Thu,T. Bastelberger, and H. Hocker in Makromol. Chem., Rapid Commun. 1981 2,pp 383-386. This reference describes the polymerization of a cyclicvinyl ether in the presence of a chromium-carbene compound undernitrogen atmosphere.

All of the transition metal catalyst and cocatalyst systems described inthe background art are deficient in that they are either moisturesensitive and/or air sensitive, or they do not teach polymerization ofcyclic olefins via olefin metathesis.

Methods employing photolysis for metathesis of olefinic compounds usingW(CO)₆ in the presence of CCl₄ have been disclosed by A. Agapiou and E.McNelis in J. Chem. Soc., Chem. Comm. 1975, 187, and by C. Tanielian, R.Kieffer, and A. Harfouch in Tetrahedron Lett. 1977, 52, 4589-4592. P.Krausz, F. Garnier, and J. Dubois in J. Oroanomet. Chem., 1978, 146,125-134 disclose photoassisted olefin metathesis of trans-2-pentene inthe presence of W(CO)₆ /CCl₄ to provide a mixture of 2-butene and3-hexene. No polymers are taught. Certain tungsten-containing compoundsand Lewis acid cocatalysts such as AlCl₃ or ZrCl₄ have also beendisclosed by T. Szymanska-Buzar and J. J. Ziolkowski in J. Mol. Cat.,1987, 43, 161-170, for metathesis of linear olefins. No polymerizationis taught. All of these systems are deficient in that they are sensitiveto air or water, employ halogen-containing cocatalysts, or do not teachthe polymerization via olefin metathesis of cyclic olefins.

SUMMARY OF THE INVENTION

The present invention provides polymerizable compositions comprising

a) at least one ring-strained non-conjugated cyclic olefin, and

b) a one-part or two-part transition metal containing catalyst which isair and moisture stable,

wherein

1) the one-part transition metal-containing catalyst is selected fromthe group consisting of

(a) compounds of the formula:

    (L.sup.1)(L.sup.2)Q

wherein

Q represents Mo or W;

L¹ represents one to six CO (carbonyl) ligands;

L² represents none to 5 ligands, each of which is a non-ionic compoundor unit of a polymer which can be the same or different, eachcontributes two, four, or six electrons to the metal and is differentfrom L¹ ;

wherein the sum of the valence electrons of Q and the electronscontributed by the ligands L¹ and L² is 18,

(b) at least one of cationic ruthenium and osmium-containingorganometallic salts having at least one polyene ligand, and

(c) [Ir(RO₂ CHC=CHCO₂ R)₂ Cl]₂ wherein each R independently is hydrogenor lower alkyl (C₁ to C₄), provided that the oxidation state of themetal is in the range of +3 to 0, and that cocatalysts containingC-halogen bonds are not present;

2) said two-part catalyst comprises

(a) a transition metal-containing catalyst, provided that the oxidationstate of the transition metal is in the range of +3 to 0, and

(b) a cocatalyst selected from the group consisting of

(i) terminal or silyl alkynes,

(ii) organosilanes containing at least ##STR4## (iii) oxidative salts oroxidative compounds containing an oxygen atom to non-oxygen atom doublebond, and

(iv) heteroatom-containing alkenes.

In another aspect, the present invention provides a method forpolymerizing ring-strained cyclic olefins comprising the steps of:

a) providing the composition as disclosed above,

b) allowing said composition to polymerize, optionally in the presenceof at least one of actinic radiation and heat.

In yet another aspect, the present invention provides the polymerizedcomposition disclosed above.

In still further aspects, the present invention provides a moldedarticle, self-supported sheet-like article, or a coating on a substratecomprising the polymerized composition previously disclosed.

Advantages of the catalyzed compositions of the present invention overthe background art include:

faster olefin metathesis rates, including shorter induction periods;

improved control over properties of polymers, such as molecular weight;

higher yields of polymers;

improved catalyst solubility;

improved catalyst stability;

greater catalyst activity in the presence of organic functional groups;

greater catalyst activity in the presence of adventitious or added wateror air;

a homogeneous composition containing the one part and two-part catalystsof the invention;

better process control, including the ability to trigger catalystactivity; and

adequate reaction rates at lower concentrations of transition metalcompound, with derivative advantages such as lower catalyst costs, lessresidual contamination or color from transition metal, and bettercontrol over polymer properties such as molecular weight.

Transition metal compounds and optional cocatalysts of the presentinvention are not sensitive to water or air. Tolerance of at leastadventitious amounts of water or air is a significant advantage in manyindustrial processes, obviating the need for expensive purificationsteps; further, in some processes such purification is not possible. Itis also advantageous to be able to manipulate and store transition metalcompounds and promoters in humid or dry air. What the background art hasnot taught that the present invention teaches are catalysts containingtransition metal compounds and optionally cocatalysts which arering-strained cyclic olefin metathesis polymerization catalysts andwhich are insensitive to water, either adventitious or as solvent orcosolvent, and to air. Further, the catalysts of the present inventionare active in the presence of many organic functional groups, notablythose containing oxygen (0), sulfur (S), or nitrogen (N) atoms.

In this application:

"ring-strained" means the conversion of monomer to polymer isexothermic, i.e., there is a negative free energy change duringconversion of monomer to polymer, as discussed by K. J. Ivin and T.Saegusa in "General Thermodynamic and Mechanistic Aspects ofRing-opening Polymerization," Chapter 1 in K. J. Ivin, T. Saegusa , eds.Ring-Opening Polymerization, Vol. 1, Elsevier: London, 1984, pp 1-3;

"actinic radiation" means electromagnetic radiation and electron beam(e-beam);

"homogeneous composition" means that the transition metal catalyst andoptional cocatalyst are soluble in at least one phase of thepolymerizable composition or in a liquid which will also dissolve thepolymerizable composition;

"organometallic" means a group containing at least one carbon totransition metal bond is present;

"oxidation state" is a formalism describing the number of d-shellelectrons associated with a transition metal, as discussed by J. P.Collman and L. S. Hegedus in Principles and Applications ofOrganotransition Metal Chemistry, University Science Books, Mill ValleyCalif., 1980, 13-19; ##STR5## or "alkenyl" all refer to carbon-to-carbondouble bonds.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS OF INVENTION

Catalysts of the present invention are useful in the synthesis ofpolymers from cyclic olefins. Optionally, certain classes of cocatalystsmay be used in combination with transition metal compounds from PeriodicGroups 4-10 (first row elements in Groups 4 to 10 are titanium (Ti),vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co),nickel (Ni), respectively), to achieve various combinations of theadvantages set forth above. Preferred are transition metal compoundsselected from Groups 6-10, more preferably Groups 6, 8 or 9. Mostpreferred are transition metal compounds of W, Ru, and Ir.

The reaction equation for the cyclic olefin metathesis polymerizationreaction is shown below. ##STR6## wherein ##STR7## means a nonconjugatedcyclic olefin monomer and ##STR8## means a ring opened polymerized unitwith the same degree of unsaturation as the monomer, and wherein n isfrom 5 to 50,000. The molecular weight of the polymers can be in therange of 300 to 5 million.

Cyclic olefins useful in compositions of the present inventionpreferably include ring-strained monocyclic olefins such as cyclobutene,cyclopentene, cycloheptene, and cyclooctene, optionally substituted withup to four saturated or unsaturated hydrocarbyl, alkaryl, aralkyl oraryl groups, in which "alkyl" or "alk" or "hydrocarbyl" may be linear,branched, or cyclic, each group containing up to thirty carbon atoms, upto sixty halogen atoms, and up to four heteroatoms selected fromnon-peroxidic 0, N, and Si, which may be combined to form functionalgroups or linkages including ether, alcohol, ketone, aldehyde,carboxylic acid, ester, amide, amino, cyano, anhydride, and the like.Also preferable are polycyclic mono- or diolefins such as norbornene,norbornadiene, and dicyclopentadiene, and oligomers thereof, andheteroatom-containing polycyclic olefins such as 7-oxanorbornene,optionally substituted with up to four saturated or unsaturatedhydrocarbyl, alkaryl, aralkyl, or aryl groups, in which "alkyl" or "alk"or "hydrocarbyl" may be linear, branched, or cyclic, each groupcontaining up to thirty carbon atoms, up to sixty halogen atoms, and upto four heteroatoms selected from nonperoxidic oxygen (0), nitrogen (N),and silicon (Si), which may be combined to form functional groups orlinkages including ether, alcohol, ketone, aldehyde, carboxylic acid,ester, amide, amino, cyano, anhydride, and the like. In the case ofsubstituted norbornene and dicyclopentadiene, endo or exo or syn or antior combinations of any of these isomers are suitable. Other examples ofsuitable monomers include norbornene, 5-methyl-2-norbornene,5-ethyl-2-norbornene, 7-methyl-2-norbornene, 1-methyl-2-norbornene,5,6-dimethyl-2-norbornene, 5-norbornene-2-carbonitrile,5-norbornene-2-carboxaldehyde, 5-norbornene-2,3-dicarboxylic acid,diethyl 5-norbornene-2,3-dicarboxylate, dimethyl5-norbornene-2,3-dicarboxylate, 5-norbornene-2,3-dicarboxylic anhydride,5-norbornene-2,2-dimethanol, 5-norbornene-2-methanol, 5-norbornen-2-ol,2-acetyl-5-norbornene, 5-norbornen-2-yl acetate, 2-benzoyl-5-norbornene,5-vinyl-2-norbornene, 5-methylene-2-norbornene, 5-norbornene-2-methanolacrylate, 5-[2-(trimethylsilyl)ethyl]-2-norbornene,5-[2-(pentamethyldisiloxy)ethyl]-2-norbornene,5-chloromethyl-2-norbornene, 2,3-di(chloromethyl)-5-norbornene,5-trifluoromethyl-2-norbornene, and2,3,3-trifluoro-2-trifluoromethyl-5-norbornene. Other suitable monomersare described in U.S. Pat. Nos. 5,011,730, 4,994,535, 4,945,144,4,943,621, 4,923,943, 4,923,936, and 4,250,063 which are incorporatedherein by reference. All these materials are commercially available(e.g., many from Aldrich Chemical Co., Milwaukee, Wis.) or theirpreparation is described in the chemical literature;5-[2-(trimethylsilyl)ethyl]-2-norbornene and5-[2-(pentamethyldisiloxy)ethyl]-2-norbornene are prepared by thereaction of 5-vinyl-2-norbornene with trimethylsilane orpentamethyldisiloxane, respectively, using published procedures andplatinum-containing catalysts for hydrosilation of alkenes (see D. A.Armitage, "Organosilanes," Chapter 9.1 in G. Wilkinson, F. G. A. Stone,and E. W. Abel, eds., Comprehensive Organometallic Chemistry, Vol. 2,Pergamon Press, Oxford, 1982, 117-120). Preferably, at least one of thecyclic olefins of the present invention is polycyclic, more preferablyit is norbornene or substituted norbornene or dicyclopentadiene, orsubstituted dicyclopentadiene.

The one-part and two-part homogeneous catalysts of the present inventioncan include the following:

For the one-part catalysts (L¹)(L²)Q wherein L¹, L², and Q are asdefined above, and which preferably has the formula Q(CO)₆, wherein Qcan be W or Mo, and substituted derivatives thereof; cationicorganometallic Ru-containing or Os-containing compounds having at leastone polyene ligand; and [Ir(RO₂ CHC═CHCO₂ R)₂ Cl]₂, all are effectivethermal or photoactivated catalysts for olefin metathesis polymerizationof ring-strained olefins. Preferably the oxidation state of thetransition metal is in the range of +3 to 0, more preferably +2 to 0,and preferably the composition is free of cocatalysts containingC-halogen bonds, especially CCl₄ and CHCl₃.

In the one-part transition metal-containing catalyst having the formula(L¹)(L²)(Q), ligands L¹ and L² are well known in the art of transitionmetal organometallic compounds. Ligands L¹ to L² are neutral, stablecompounds, and each contributes an even number of electrons to the metalQ, which can be Mo or W. Ligands L¹ to L² are stable non-ionic compoundsor polymeric units in and of themselves (they are not salts, groups,radicals or fragments) and can exist independently of the organometalliccompound without special conditions, and they are stable at roomtemperature.

Ligand L¹ is only carbonyl, CO.

Ligands L² are provided by monodentate and polydentate compounds(preferably containing up to about 30 carbon atoms and up to 10 heteroatoms selected from nitrogen, sulfur, non-peroxidic oxygen, phosphorus,arsenic, selenium, antimony, and tellurium). Examples of suitablemonodentate compounds or groups are carbon sulfide, carbon selenide,carbon telluride, alcohols such as ethanol, butanol, and phenol; etherssuch as tetrahydrofuran; compounds of Group VA elements such as ammonia,phosphine, trimethylamine, trimethylphosphine, triphenylamine,triphenylphosphine, triphenylstilbine, triphenylarsine,tributylphosphite; isonitriles such as phenylisonitrile,butylisonitrile; olefinic compounds such as ethylene, acetylene,propylene, methylacetylene, 1-butene, 2-butene, diacetylene,1,2-dimethylacetylene, cyclobutene, pentene, norbornene, cyclopentene,hexene, cyclohexene, cycloheptene, 1-octene, 4-octene,3,4-dimethyl-3-hexene, 1-decene, i-dodecene;

suitable polydentate compounds or groups include1,2-bis(diphenylphosphino)ethane, 1,2-bis(diphenylarsino)ethane,bis(diphenylphosphino)methane, ethylenediamine, propylenediamine,diethylenetriamine, hydridotripyrrazolyborate, butadiene, norbornadiene,1,3-cyclohexadiene, cyclopentadiene, and 1,4-cyclohexadiene.

The ligand L² can be a unit of a polymer, for example the coordinatingamino group in poly(ethyleneamine); the coordinating phosphino group inpoly(4-vinylphenyldiphenylphosphine); and the coordinating isonitrilegroup in poly(4-vinylphenylisonitrile). Polymers having a weight averagemolecular weight up to 1,000,000 or more can be used. It is preferablethat 5 to 50 percent of the coordinating groups present in the polymerbe complexed with the metal.

Further illustrative of ligand L² are substituted and unsubstitutedcycloheptatriene, cyclooctatetraene, benzene, toluene, xylenes,mesitylene, hexamethylbenzene, fluorene, naphthalene, anthracene,perylene, chrysene, pyrene, triphenylmethane and carbocyclic andheterocyclic aromatic ligands having up to 25 rings and up to 100 carbonatoms and up to 10 hetero atoms selected from nitrogen, sulfur,non-peroxidic oxygen, phosphorus, arsenic, selenium, boron, antimony,tellurium, silicon, germanium, and tin.

The ligand L² can be a unit of a polymer, for example, the phenyl groupin polystyrene, poly(styrene-co-butadiene), poly(styrene-co-methylmethacrylate), poly(alpha-methylstyrene), polyvinylcarbazole, andpolymethylphenylsiloxane; the cyclopentadiene group inpoly(vinylcyclopentadiene), etc. Polymers having a weight averagemolecular weight up to 1,000,000 or more can be used. It is preferablethat 5 to 50 percent of the unsaturated or aromatic groups present inthe polymer be complexed with the metal.

Each of the ligands L² can be substituted by groups that do notinterfere with the complexing of the ligand with the metal atom.Examples of substituting groups, all of which preferably have less than30 carbon atoms and up to 10 hetero atoms selected from nitrogen,sulfur, non-peroxidic oxygen, phosphorus, arsenic, selenium, antimony,tellurium, silicon, germanium, tin, and boron, include hydrocarbylgroups such as methyl, ethyl, butyl, dodecyl, tetracosanyl, phenyl,benzyl, allyl, benzylidene, ethenyl, and ethynyl; hydrocarbyloxy groupssuch as methoxy, butoxy, and phenoxy; hydrocarbylmercapto groups such asmethylmercapto (thiomethoxy), phenylmercapto (thiophenoxy);hydrocarbyloxycarbonyl such as methoxycarbonyl and phenoxycarbonyl;hydrocarbylcarbonyl such as formyl, acetyl, and benzoyl;hydrocarbylcarbonyloxy such as acetoxy, and cyclohexanecarbonyloxy;hydrocarbylcarbonamido, e.g., acetamido, benzamido; azo, boryl; halo,e.g., chloro, iodo, bromo, and fluoro; hydroxy; cyano; nitro; nitroso,oxo; dimethylamino; diphenylphosphino, diphenylarsino; diphenylstibine;trimethylgermane; tributyltin; methylseleno; ethyltelluro; andtrimethylsiloxy; condensed rings such as benzo, cyclopenta; naphtho,indeno; and the like.

Preferably, the one-part catalyst containing Mo or W is Mo(CO)₆, Mo(CO)₄(norbornadiene), W(CO)₆, and (mesitylene)W(CO)₃.

The cationic ruthenium and osmium organometallic compounds which can bethe one-part catalyst of this invention contain at least one cyclic oracyclic polyene ligand directly bonded to the Ru or Os atom. Preferably,the polyene ligand is benzene or an aromatic benzene derivative such ascymene.

One representative group of ruthenium and osmium cations of thisinvention are of the formula (Ar)M(N.tbd.CR³)₂ X⁺ where Ar is benzene orany of the alkyl, ether, or formate substituted benzenes such astoluene, ortho-, meta-, or para-xylene, mesitylene, ortho-, meta-, orpara-cymene, durene, isodurene, hexamethylbenzene, pentamethylbenzene,cumene, pseudocumene, prehnitene, triethylbenzene, anisole, methyl2-methylbenzoate, ethyl benzoate, or 2-, 3-, or 4methylanisole; M isruthenium or osmium; R3 is a linear or branched hydrocarbon chain with 1to 30 carbon atoms; and X is a halogen chosen from Cl, Br, or I. Theseruthenium and osmium cations are derived from [(Ar)RuX₂ ]₂ (prepared bythe method described by M. A. Bennett and A. K. Smith in J. Chem. Soc.,Dalton Trans. 1972, pp 233-241) or [(Ar)OsX₂ ]₂ (prepared by the methodsdescribed by J. A. Cabeza and P. M. Maitlis in J. Chem. Soc., DaltonTrans. 1985, pp 573-578 and M. Brown, X. L. R. Fontaine, N. N. Greenwoodand J. D. Kennedy in J. Organomet. Chem. 1987, 325, pp 233-246) where Arand X are the same as described above. Suitable counterions include PF₆⁻, AsF₆ ⁻, BF₄ ⁻, SbF₆ ⁻, and the like. Suitable halogen abstractingreagents include AgBF₄, KAsF₆, TlPF₆, LiBF₄, NH₄ PF₆, and the like.

Another group of ruthenium and osmium cations of this invention are ofthe formula (Ar)M(Py)₂ X⁺ where Ar, M, and X are as described above andPy is pyridine or a substituted pyridine such as 2-, 3-, or4-acetylpyridine, 2-, 3-, or 4-benzylpyridine, 3,4-lutidine,3,5-lutidine, 2-, 3-, or 4-bromopyridine, 2-, 3-, or 4-ethylpyridine,3-, or 4-phenylpyridine, and the like. These complexes may be preparedby the methods described by T. Arthur and T. A. Stephenson in J.Organomet. Chem. 1981, 208, pp 369-387.

Also useful in this invention is another group of ruthenium and osmiumcations of the formula (Ar)M-(μ-Y)₃ -M(Ar)⁺ where each Ar isindependently defined the same as for Ar above; each M may be the sameor different but is Ru or Os; and Y is chosen from the group consistingof Cl, Br, I, H, OH, and ER⁴ where R⁴ is a linear or branchedhydrocarbon chain with 1 to 30 carbon atoms or an aromatic groupcontaining 6 to 20 carbon atoms and E is oxygen (O) or sulfur (S). Thethree Y groups bridge the M atoms and there is no M bond, further, thethree Y groups need not be identical but may consist of a combinationCl, Br, I, H, OH, and ER⁴ groups. A variety of synthetic routes to thesecomplexes exists in the literature and are summarized by H. Le Bozec, D.Touchard, and P. H. Dixneuf in Adv. Organomet. Chem. 1989, 29, pp163-247.

Counterions are required in all the cationic ruthenium and osmiumorganometallic compounds containing at least one cyclic or acyclicpolyene ligand directly bonded to the Ru or Os and representativecounterions include PF₆ ⁻, AsF₆ ⁻, BF₄ ⁻, SbF₆ ⁻, and the like.

Other ruthenium and osmium compounds, both neutral and cationic, are ofuse in the present invention and include (Ar)OsX₂ (N.tbd.CR³),[(CHT)RuX₂ ]₂, (CHT)RuCl(CH₃ CN)₂ ⁺¹, (Ar)Ru(Ch₃ CN)₃ ⁺², CpRu(CH₃ CN)₃⁺¹,[(COD)RuX₂ ]_(x), (COD)RuX(CH₃ CN)₃ ⁺, (Ar)RuCl(alyl), (COD)RuX₂ (CH₃CN)(CO), (diene)RuCl₂ (amine)₂, CpRu(diene)Cl, [CpRu(Cl)₂ ]_(x), (CP^(*)Ru(Cl)₂ ]_(x), [(1-3-η:6-8-η)-2,7-dimethyloctadienediyl)RuCl₂ ]₂ and thelike where Ar, X, and R³ are as defined above; CHT is cycloheptatriene;COD is 1,5-cyclooctadiene; Cp is eta⁵ -cyclopentadienyl; Cp^(*) ispentamethylcyclopentadienyl; diene is a cyclic or acyclic hydrocarboncontaining 4 to 30 carbon atoms further containing two carbon-to-carbondouble bonds; amine is primary, secondary or tertiary aliphatic amine,and allyl is the eta-3 bound ##STR9## ligand or any of its derivatives.

The two-part catalyst comprises

(a) a transition metal-containing catalyst, provided that the oxidationstate of the transition metal is in the range +3 to 0, preferably +2 to0,

(b) a cocatalyst selected from the group consisting of

(i) terminal and silyl alkynes (e.g., --C.tbd.C--H or--C.tbd.C--Si(R¹)₃, wherein R¹ is defined below), preferably a terminalalkyne, most preferably phenylacetylene,

(ii) organosilanes containing at least one of ##STR10## (iii) oxidativesalts or oxidative compounds containing an oxygen to non-oxygen doublebond,

(iv) heteroatom-containing alkenes, preferably enamines, vinyl ethers,or vinyl thioethers, and more preferably vinyl ethers.

The four two-part catalysts are designated classes I to IV as follows:

I. Transition metal compound plus terminal alkyne cocatalyst:

Preferably, the transition metal compound to be used in combination withan alkyne cocatalyst can be selected from Periodic Groups 6 to 9compounds, more preferably compounds containing Mo, W, Ru or Ir. Mostpreferably, it is free of metal-carbon multiple bonds.

The alkyne cocatalyst can be represented by Formula I.

    R.sup.1 C.tbd.CR.sup.2                                     I

where R¹ is hydrogen, or saturated or unsaturated hydrocarbyl, alkaryl,aralkyl, aryl, perfluoroalkyl, perfluoroaryl, or silyl group, all ofthese groups containing up to 30 carbon atoms and up to four heteroatomsselected from O, N, and Si, and R² is hydrogen (H) or silyl (i.e.,--Si(R¹)₃, wherein R¹ is as defined above). Preferably R² is H and thesecompounds are known as terminal alkynes. Illustrative examples of suchterminal alkynes include acetylene, phenylacetylene, 1-hexyne, 1-octyne,3,3-dimethyl-1-butyne, 2-methyl-1-buten-3-yne, 1,7-octadiyne, propargylchloride, propargyl alcohol, methyl propargyl ether,3-methoxy-3-methyl-1-butyne, 1 methoxy-1-buten-3-yne,2-methyl-3-butyn-2-ol, 1-ethynylcyclohexylamine, monopropargylamine,1-dimethylamino-2-propyne, tripropargylamine, 3-butyne-2-one, propiolicacid, methyl propiolate, bromoacetylene, trimethylsilylacetylene, and3,3,3-trifluoropropyne. Examples of silyl alkynes are1-trimethylsilyl-1-propyne, bis-trimethylsilylacetylene, and ethyl3-(trimethylsilyl)-1-propynoate. These compounds are commerciallyavailable or are described in the chemical literature.

The combination of transition metal compounds and terminal alkynecocatalysts of this invention can provide faster rates of olefinmetathesis polymerization, shorter induction periods and higher polymeryields than the corresponding systems containing no cocatalyst.

II. Transition metal compound plus organosilane containing ##STR11##group cocatalyst:

Preferably, the transition metal compound to be used in combination withthe organosilane cocatalyst is selected from Groups 6 to 9, morepreferably Ru and Ir, most preferably Ir.

Organosilane cocatalysts of the present invention are compoundscontaining from 1 to 20 silicon atoms, containing up to 100 carbon atomsand optionally containing up to 20 heteroatoms selected fromnon-peroxidic O and N, and further containing at least one of silylhydride ##STR12## and silyl alkenyl, the alkenyl group containing up to12 carbon atoms and incorporating at least one ##STR13## bond. The silylalkenyl group preferably is silyl vinyl, i.e., ##STR14## Theorganosilane may also contain other carbon-containing groups includinghalogenated and non-halogenated alkyl, alkaryl, aralkyl, and aryl groupshaving up to 30 carbon atoms, 60 halo atoms, and 4 heteroatoms selectedfrom 0, N, and Si, such as methyl, ethyl, hexyl, octadecyl, cyclohexyl,phenyl, 4-methylphenyl, phenylethyl, 3,3,3-trifluoropropyl, and4-chlorophenyl. Organosilane cocatalysts suitable for the practice ofthe present invention containing at least one Si-H group includetriethylsilane, diethylsilane, phenyldimethylsilane, phenylmethylsilane,phenylsilane, pentamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane,1,1,1,3,3,5,5-heptamethyltrisiloxane,1,1,1,3,5,5,5-heptamethyltrisiloxane, and1,1,3,3,5,5-hexamethyltrisiloxane. Organosilicon cocatalysts suitablefor the practice of the present invention containing at least onesilyl-alkenyl group include vinyltrimethylsilane, tetravinylsilane1,3-divinyltetramethyldisiloxane,1,3-bis(5-hexenyl)tetramethyldisiloxane, and1,3,5,7-tetravinyltetramethylcyclotetrasiloxane. These compounds arecommercially available or can be synthesized as described below.

The use of organosilane cocatalyst can provide advantages such asincreased catalyst activity, shorter induction periods, and inparticular greater catalyst solubility in polymerizable compositions andmore stable catalysts and catalyst solutions.

In a further aspect, organosilane cocatalyst, when used in amountsranging from 0.5 to 1000 moles, preferably 0.5 to 100, per mole oftransition metal compound in a reaction mixture containing polymerizablecyclic olefin, can also provide improved control over molecular weightof the resulting polymer, that is, molecular weights are lower than inthe absence of organosilane. Lower molecular weights can be desirable;in particular, solutions of very high molecular weight polymer can bevery viscous and difficult to process.

III. Transition metal compound plus oxidative cocatalyst:

Preferably, the transition metal compound to be used in combination withan oxidative cocatalyst is selected from compounds containing Groups 6to 9 transition metals, more preferably compounds wherein the metal canbe Mo, W, Ru or Ir.

Oxidative cocatalysts of the present invention can be inorganic,organometallic or organic. They are selected from oxidative salts andcompounds containing at least one oxygen to non-oxygen double bond.

Oxidative salts useful as cocatalysts in the present invention arecationic salts, with the further provision that the counteranion of thesalt cannot be a single halogen atom. Examples of cations suitable inthe present invention include Ag⁺, Na⁺, Cu⁺², Zn⁺², Cp₂ Fe⁺ (Cp is eta⁵-cyclopentadienyl; this cation is called ferricinium), Ph₃ C⁺ (trityl),and tris(4-bromophenyl)aminium, Ph₂ I⁺ (wherein Ph=phenyl) Tl⁺, NO⁺, NP₂⁺, Ph₃ S⁺, Cu⁺, tropylium, and the like. Preferred cations are Ag⁺, Cp₂Fe⁺, trityl and tris(4bromophenyl)aminium. Suitable counteranionsinclude PF₆ ⁻, SbF₆ ⁻, AsF₆ ⁻, BPh₄, BF₄ ⁻, SbCl₆ ⁻, and the like.

Representative examples of oxidative salts which are commerciallyavailable or are described in the chemical literature include: Ag⁺ BF₄⁻, Ag⁺ PF₆ ⁻, Ag⁺ SbF₆ ⁻, Ag⁺ AsF₆ ⁻, Na⁺ PF₆ ⁻, Na³⁰ SbF₆ ⁻, Zn⁺² (BF₄⁻)₂, Cp₂ Fe⁺ PF₆ ⁻, Ph₃ C⁺ PF₆ ⁻, tris(-4bromophenyl)aminium⁺ SbF₆ ⁻,and the like. Preferred oxidative salts are those used in Examples 8 to11, below.

Suitable examples of oxidative cocatalysts containing oxygen tonon-oxygen double bonds are iodosobenzene, trimethylamine oxide,benzophenone, 1,4-benzoquinone, and the like. O₂ gas is not includedwithin this class of cocatalysts; further, the concentration andpresence of O₂ are difficult to control, and undesirable side reactionsmay occur if O₂ is present in high concentrations such as might beachieved when it is deliberately bubbled through a reaction mixture.

Oxidative cocatalysts useful in the present invention are commerciallyavailable or are described in the chemical literature.

Oxidative cocatalysts of the present invention can provide advantages interms of faster metathesis rates, reduced induction periods, betteryields, and, in particular, better tolerance of organic functionalgroups which may be present as groups on the cyclic olefin monomer or asgroups on other additives to the reaction mixture, such as solvents.

The term "oxidative" cocatalyst is used because, while not wishing to bebound by theory, we believe that this class of cocatalysts functions byoxidizing the transition metal compound or materials derived therefrom,including transition metal compounds formed in the presence of olefin,in one or more steps. Oxidation is used here to refer to any processwhich removes at least one of electrons, atoms or groups from atransition metal compound, thereby leaving the transition metal compoundin a configuration with fewer electrons. The formalisms for determiningelectron configuration, that is oxidation state and coordination number,are described by J. P. Collman and L. S. Hegedus in Principles andApplications of Organotransition Metal Chemistry, University ScienceBooks, Mill Valley Calif., 1980, 13-19, and are well known to thoseskilled in the art.

IV. Transition metal compound plus heteroatomcontaining alkene:

Preferably, the transition metal compound to be used in combination witha heteroatom-containing alkene is selected from compounds containingGroups 6 to 9 metals, more preferably Mo, W, Ru, or Ir.

Effective cocatalysts of this class, which are commercially availableare described in the chemical literature, include heteroatom substitutedlinear, branched or cyclic alkenes having up to 30 carbon atoms whereinthe heteroatoms are alpha to the olefinic unsaturation and are selectedfrom nitrogen, non-peroxidic oxygen, and sulfur, preferably nitrogen andnon-peroxidic oxygen, most preferably non-peroxidic oxygen. Optionally,these compounds may contain up to 10 aryl groups, each of which maycontain up to 20 carbon atoms and 4 heteroatoms. Olefinic compounds withheteroatom substitution in positions other than the alpha position arealso considered cocatalysts of the present invention if they are able toundergo isomerization in the presence of transition metal olefinmetathesis catalysts to give olefins with heteroatoms in the alphaposition. Olefin isomerization in the presence of transition metalcompounds is well known to those skilled in the art.

For olefins with nitrogen as the alpha heteroatom, the nitrogen isamino-type nitrogen. These olefins belong to the group of compoundsreferred to as enamines and contain the ##STR15## group. Illustrativeexamples of enamines include 2-pyrrole, pyrrole,1-pyrrolidino-1-cyclohexene, 1-pyrrolidino-1-cyclopentene,1-morpholino-1-cyclohexene, and the like.

For olefins with oxygen as the alpha heteroatomic group, the oxygen is anon-peroxidic, ether-type oxygen. These olefins belong to the group ofcompounds referred to as vinyl ethers and contain the ##STR16## group.Illustrative examples of vinyl ethers include 3,4-dihydro-2H-pyran,2,3-dihydrofuran, furan, 5,6-dihydro-4-methoxy-2H-pyran,3,4-dihydro-2-methoxy-2H-pyran, methyl vinyl ether, ethyl vinyl ether,n-butyl vinyl ether, t-butyl vinyl ether.

For olefins with sulfur as the alpha heteroatom, the sulfur is adivalent thioether-type sulfur. These olefins belong to the group ofcompounds referred to as vinyl thioethers and contain the ##STR17##group. Illustrative examples of vinyl thioethers include thiophene,2-methylthiophene, 3-methylthiophene, 1,2-dihydrothiophene, vinyl methylsulfide, vinyl butyl sulfide.

For non-alpha heteroatomic group substituted olefins, the heteroatomicgroups are the same as those specified above. These olefins are capableof rearrangement to alpha heteroatomic group substituted olefins in thepresence of transition metal olefin metathesis catalysts. Thus7-oxanorbornene (7-oxabicyclo[2.2.1]hept-5-ene), an allyl ether, wouldnot be considered a cocatalyst of the present invention as thebridgehead carbons preclude isomerization to the vinyl ether structure.Illustrative examples of non-alpha heteroatomic group substitutedolefins that are cocatalysts of the present invention include2,5-dihydrofuran, 1,3-dioxep-5-ene, 3-pyrroline, allyl sulfide,allylamine, allylcyclohexylamine, allyl ether, allyl ethyl ether, allylmethyl sulfide, allyl propyl ether.

Compositions comprising a transition metal compound and aheteroatom-containing alkene can provide advantages such as faster ratesof olefin metathesis polymerization, shorter induction periods, andhigher yields of polymer.

The polymerizable composition comprising a transition metal compound, anoptional cocatalyst, and a monomer may further contain compoundscontaining organic functional groups such as alcohol, anhydride,carboxylic acid, ether, aromatic ring, ketone, ester, cyano, amide,amine, phosphine, sulfide, thiol, and the like; such compounds may benaturally occurring or present as impurities, or may have beendeliberately added to one of the components such as a solvent,stabilizer, antioxidant, pH adjuster, colorant, pigment or dye, filler,flow agent, plasticizer, tackifier, flow agent, emulsifier, and thelike. Nonreactive solvents may optionally be employed, and these maycontain functional groups as described above. These optionally presentadjuvants can be present in an amount up to 90 percent by weight,preferably up to 50 percent by weight.

Transition metal compounds may be employed in amounts ranging from0.0001 to 10 percent by weight of the total polymerizable composition,preferably 0.0005 to 5 percent, most preferably 0.0005 to 2 percent.

Optionally, cocatalysts of the present invention may be added.Cocatalysts may be present in amounts ranging from 0.001 to 1000 moleper mole of transition metal-containing compound, preferably 0.01 to 100mole, most preferably 0.1 to 10 mole, provided that the total amount oftransition metal compound and cocatalyst do not exceed 20 percent byweight of the total polymerizable composition, preferably the cocatalystdoes not exceed 5 percent, most preferably not to exceed 2 percent.

In preparing compositions of the present invention, transitionmetal-containing compounds, monomers, optional cocatalysts, and anyoptional adjuvants may be mixed in any order. Olefin metathesis mayproceed at temperatures ranging from approximately -78° to 400° C.,preferably 0° to 300° C., most preferably 15°-150° C. Those skilled inthe art will recognize that faster reaction rates may be obtained athigher temperatures, so long as the catalyst does not thermallydecompose under the reaction conditions. The method may optionallyemploy activation by photolysis, that is, faster rates or improvedyields or other advantages may be achieved by irradiation of one or moreof the components of the reactive mixture, in any combination and in anyorder relative to the rest of the process. Specific advantages ofmethods employing photolysis will be discussed below. A two-stageprocess, photolysis followed by heating, may be preferred.

In a preferred embodiment, with polymerizable compositions employing theone-part catalyst disclosed above, actinic radiation may be employed toimprove catalyst activity. No cocatalyst is required, in contrast tophotoactivated olefin metathesis catalysts of the background art whichrequire a halogen-containing cocatalyst such as carbon tetrachloride,AlCl₃ or ZrCl₄. The present invention compositions are free of thesecompounds. Transition metal compounds of the present inventionpreferably possess a photochemically labile ligand. Photochemicallylabile ligands suitable in the practice of the present invention includecarbon monoxide, azide, nitriles, oxalate, arenes, olefins, dihydrogen,phosphines, phosphites, and the like. Other photolabile groups will beapparent to those skilled in the art. Preferred photolabile ligandsinclude carbon monoxide, arenes, nitriles, and olefins and diolefinssuch as cyclooctadiene, norbornadiene, and ethylene. Useful compoundscontaining these ligands are commercially available or are described inthe chemical literature.

Compositions and methods of the present invention, which employ actinicradiation can provide advantages such as faster rates of polymerization.The production of more active catalysts upon photolysis is particularlyadvantageous, providing substantial improvements in process controlbased upon the ability to trigger catalyst activity. That is, a reactionmixture can be prepared and maintained in an unpolymerized state so longas it is protected from actinic radiation, and can then be caused topolymerize at a desired time or place in a process by irradiation. Theprocess requirements and advantages of photogenerated catalysts areapparent to those skilled in the art.

In another embodiment, the methods for polymerizing the compositions ofthe present invention described above may employ heat.

Optionally, cocatalysts may be used with thermal or photochemicallyactive transition metal compounds to provide improved catalystreactivity or performance.

Polymers formed via olefin metathesis polymerization of cyclic monomersare useful as molded articles, elastomers, dielectric supports,ionophoric or biologically active materials, composite materials, coatedarticles, and the like. The polymerizable or polymerized compositionscan be coated by means known in the art onto supports such as polymers,paper, metals, glass, and ceramics.

Objects and advantages of this invention are further illustrated by thefollowing examples, but the particular materials and amounts thereofrecited in these examples, as well as other conditions and detailsshould not be construed to unduly limit this invention.

EXAMPLES

Throughout these examples, the following abbreviations are used:

NB=norbornylene (bicyclo[2.2.1]hept-2-ene)

NBD=norbornadiene

GBL=gamma-butyrolactone

Ru-1=[Ru(cymene)Cl₂ ]₂

Ru-2=[(C₆ H₆)Ru(CH₃ CN)₂ Cl]⁺ PF₆ ⁻

Ir-1=Ir(COD)Cl]₂

Ir-2=commercial [Ir(cyclooctene)₂ Cl]₂

Ir-3=Ir(CO)₂ (acac)

CP=eta⁵ -cyclopentadienyl

Cp*=pentamethylcyclopentadienyl

COD=1,5-cyclooctadiene

acac=acetylacetonate

cat=catalyst

cocat=cocatalyst

samp=sample

Me=methyl

Et=ethyl

Bu=butyl

Ph=phenyl

NM=not measured

Except as noted, all materials used in these examples are available fromAldrich Chemical Company, Milwaukee, Wis. N₂ Owas obtained from MathesonGas Products, East Rutherford, N.J. All organosilane cocatalysts and3-trimethylsilylcyclopentene are available from Petrarch Systems,Bristol, Pa. Ir-1 and Ir-3 are available from Strem Chemicals, Inc.,Newburyport, Mass. Iodosobenzene is available from Pfaltz and Bauer,Inc., Waterbury, Conn. Cyclohexylacetylene is available from FlukaChemical Corp., Ronkonkoma, N.Y. Cu(BF₄)₂ (45% in H₂ O) is availablefrom Allied Chemical, Morristown, N.J.

Cp₂ Fe⁺ PF₆ ⁻ can be prepared by methods found in the chemicalliterature, such as J. C. Smart, B. L. Pinsky, J. Amer. Chem. Soc. 1980,102, 1009-1015.

Preparation of 1,3-bis(5-hexenyl)tetramethyldisiloxane was as follows: A1-L 3-necked round bottom flask equipped for magnetic stirring andfitted with a thermometer, a reflux condensor, and an addition funnelwas flushed with nitrogen and charged with 297.9 g of 1,5-hexadiene andapproximately 30 mg of a 15 wt % solution of platinum(O) in1,3-divinyl-1,1,3,3-tetramethyldisiloxane. The addition funnel wascharged with 218.3 g of 1,1,3,3-tetramethyldisiloxane. The flask and itscontents were warmed to a temperature of 60° C., and the1,1,3,3-tetramethyldisiloxane was added dropwise with stirring over aperiod of 6 hours. After the addition was complete, the reaction mixturewas maintained at 60° C. for an additional 1 hour. Approximately 2 g ofacrylonitrile and 2 g of activated carbon were added to complex theplatinum catalyst, and the mixture was cooled to room temperature andstirred overnight. The reaction mixture was filtered, and distillationof the filtrate yielded 133.9 g (34%) of the desired product (bp 77°-78°C., 0.07 mm) as a clear, colorless liquid.

Solvents used were reagent or spectroscopic grade, and were used withoutfurther purification. All commercially available materials were usedwithout further purification. [Ir(cyclooctene)₂ Cl]₂ is labeled as "airsensitive" but was handled and stored in air after it was received.

Note that all the monomers, catalysts, cocatalysts, and solvents can bemanipulated and used in air without incident or disadvantage. Also notethat moisture and air were not removed from polymerizable compositions,or else air was removed only partially (as noted), although thetransition metal compounds and optional cocatalysts were also active inthe rigorous absence of water and air.

Various Procedures were employed for reactions. Throughout the examples,these Procedures are as follows:

Procedure 1: Transition metal compound, in the amount specified,typically 1 to 50 mg, as a solid or solution as specified, was placed ina reaction vessel in air. Cocatalyst, used as specified, was added. Asolution of cyclic monomer, which was norbornene unless otherwisespecified, 25% by weight in solvent, in the amount specified, was thenadded, and the time to form a polymer was measured from the time ofaddition of monomer. All times are reported in minutes, unless otherwisespecified.

The reaction was allowed to proceed at ambient temperature (20°-25° C.)and in ambient light (room light). Polymer formation was indicated byone of three methods, as follows:

1-A: when the specified solvent dissolved norbornene but was a poorsolvent for polynorbornene formed via olefin metathesis, polymer wasinitially observed by a cloudy appearance, followed by formation ofpolymer precipitate. Such solvents included ethanol, petroleum ether,and ethyl acetate.

1-B: when the specified solvent dissolved norbornene and was a goodsolvent for polynorbornene formed via olefin metathesis, and thereaction was sufficiently slow, formation of polymer was detected byremoving a small aliquot (several drops) of reaction solution, andadding it dropwise to ethanol. Strands of white solid polymer wereobserved when polymer had formed. Solvents employing this methodincluded CH₂ Cl₂ and toluene.

1-C: when the specified solvent dissolved norbornene and was a goodsolvent for polynorbornene formed via olefin metathesis, and thereaction was too fast to allow differentiation by method 1-B, the timeto form a viscous solution, or, next, to form a "gel" (defined here as areaction mixture too viscous to flow), or, next, to produce an exotherm(observable increase in reaction mixture temperature as a result of anegative free energy change upon polymerization) were measured.

Polymer yields were determined by removal of all volatile substances(solvent and unreacted monomer) under vacuum. Molecular weights ofpolymers so obtained were determined by gel permeation chromatography(GPC) using polystyrene standards.

Procedure 2: Same as Procedure 1, except that the reaction vessel washeated to the temperature indicated.

Procedure 3: Same as Procedure 1, except that some oxygen was removedfrom the polymerizable composition by the technique of bubbling nitrogenor argon through it This technique does not remove significant amountsof water.

Procedure 4: Same as method 1, except the polymerizable composition wasirradiated with an ultraviolet lamp with a primary output of 366 nmunless otherwise indicated (Spectroline Model EN-280L, SpectronicsCorporation, Westbury N.Y.; or Model UVGL-25 Mineralight® Lamp,Ultraviolet Products Incorporated, San Gabriel, CA, which can be used toirradiate at 366 or 254 nm; or two 15 watt Black Lights, BL or BLB,General Electric, Cleveland, Ohio or Phillips, Somerset, N.J. orSylvania/GTE, Exeter, N.H.) unless otherwise specified. Depending onsolvent, polymer was observed by a method analogous to those describedin Procedure 1, that is, a cloudy appearance due to precipitation frompoor reaction solvent (4-A), precipitation from an aliquot in goodsolvent added to ethanol (4-B), or viscosity increase, gelation orexotherm (4-C).

Procedure 5: Same as Procedure 3, except that the polymerizablecomposition was irradiated with ultraviolet light (as in Procedure 4).

Departures from these procedures are indicated as appropriate.

EXAMPLE 1

This example demonstrates synthesis of (Ar)M(N.tbd.CR³)₂ X⁺ catalysts ofthe present invention.

The [(η⁶ -C₆ H₆)RuCl₂ ]₂ complex was prepared as in M. A. Bennett and A.K. Smith in J. Chem. Soc., Dalton Trans., 972, 233-241. This complex(0.50 g, 1.00 mmol) and a 1.0 molar CH₃ CN solution of LiBF₄ (2.10 mL,2.10 mmol) were placed in 25 mL of CH₃ CN in an Erlenmeyer flask. Nospecial precautions were taken to exclude air. The reddish suspensionwas stirred for 12h and was then filtered to remove a colorlessprecipitate. The orange filtrate was evaporated to a solid which wastwice fractionally crystallized (by allowing ethyl ether to slowlydiffuse into the a CH₃ CN solution of the product) to give 0.63 g (82%)of [(η⁶ -C₆ H₆)RuCl(CH₃ CN)₂ ]⁺ BF₄ ⁻ as well formed orange prisms.Spectroscopic and elemental analyses confirmed the presence of thedesired compound.

The [(η⁶ -C₆ H₆)RuCl₂ ]₂ complex (0.50 g, 1.00 mmol) and NH₄ PF₆ (0.34g, 2.10 mmol) were suspended in 25 mL of CH₃ CN and stirred 12 h.Reaction work-up as above yielded 0.74 g (84%) of [(η⁶ -C₆ H₆)RuCl(CH₃CN)₂ ]PF₆ ⁻ as orange crystals. Spectroscopic and elemental analysesconfirmed the presence of the desired compound.

The [(η⁶ -C₆ H₆)RuCl₂ ]₂ complex (0.50 g, 1.00 mmol) and KAsF₆ (0.48 g,2.10 mmol) were reacted as above to give 0.88 g (91%) of [(η⁶ -C₆H₆)RuCl(CH₃ CN)₂ ]⁺ AsF₆ ⁻ as yellow-orange needles. Spectroscopic andelemental analyses confirmed the presence of the desired compound.

EXAMPLE 2

This example illustrates the use of one-part Group containing catalysts.

[Ir(RO₂ CHC═CHCO₂ R)₂ Cl]₂ wherein each R is ethyl or H, was preparedaccording to the method described for synthesis of Ir-2 by A. van derEnt, and A. L. Onderdelinden in Inorganic Synthesis 28, 90-92) using 0.5g K₃ IrCl₆ (hydrate), 7.5 mL H₂ O, 2.5 mL 2-propanol, and 1.7 mL ofdiethyl maleate in place of cyclooctene, maintaining the reactionmixture under nitrogen at 70°-75° C. for 4 hr. A small portion of H₂ Owas added, and the water/propanol solution drawn off with a pipette. Anoily residue remained, which spectroscopic and elemental analyses showedcontained a small amount of unreacted diethyl maleate, some --CO₂ Hgroups (from hydrolysis of ethyl ester) and some --CO₂ Et groups and19-20% by weight of iridium.

Two mg of this product was placed in 10 mL NB in ethyl acetate(Procedure 1), and resulted after 8 min in a polymer precipitate whichentirely filled the reaction vessel and a noticeable exotherm. Forcomparison, an identical trial, but using as catalyst Ir-2, required 16min to yield the same results.

Examples 3 and 4 illustrate the advantages of using terminal alkynecocatalysts.

EXAMPLE 3

This example illustrates the use of terminal alkyne cocatalysts, usingProcedure 1, with 5 mg Ru-1 in 10 mL NB, 25% by weight in CH₂ Cl₂.Sample B contained 5 microliters phenylacetylene cocatalyst. The data isshown in Table A, below.

                  TABLE A                                                         ______________________________________                                        Alkyne Cocatalysts                                                            Sam- Cata-                           Time to form                             ple  lyst    Cocatalyst                                                                              Solvent                                                                              Method polymer (min)                            ______________________________________                                        A*   Ru-1    (none)    CH.sub.2 Cl.sub.2                                                                    1-A    15                                       B    Ru-1    PhC═CH                                                                              CH.sub.2 Cl.sub.2                                                                    1-A     2                                       ______________________________________                                         *comparative                                                             

The data of Table A show that polymerization is faster (Sample B fasterthan A) in the presence of terminal alkyne cocatalyst.

EXAMPLE 4

This example illustrates the use of terminal alkyne cocatalysts, with amethod employing photolysis. Procedure 5 was used, with 25 mg of W(CO)₆catalyst, 1.0 g NB, and 2 mL solvent as indicated for Samples A to D,and 30 mg W(CO)₆ in 2 mL NBD (no solvent) for samples E to J.Polymerization rates were determined by measuring the time to form agel. Sample A was not irradiated, and is presented for purposes ofcomparison. Sample B is also presented for purposes of comparison. Thedata is shown in Table B, below.

                  TABLE B                                                         ______________________________________                                        Terminal alkyne cocatalysts,                                                  with method employing photolysis                                              Sam-                        Yield, Time (min.)                                ple  Solvent  Cocatalyst    %      to gel                                     ______________________________________                                        A.sup.a *                                                                          CH.sub.2 Cl.sub.2                                                                      PhC.tbd.CH     0     (no gel formed)                            B*   CH.sub.2 Cl.sub.2                                                                      (none)        50     ≦200                                C*   CH.sub.2 Cl.sub.2                                                                      PhC.tbd.CH    >95    NM                                         D    toluene  PhC.tbd.CH    89     NM                                         E    (none)   (none)        NM      110                                       F    (none)   PhC.tbd.CH    NM      25                                        G    (none)   (4-tolyl)C.tbd.CH                                                                           NM      20                                        H    (none)   (cyclohexyl)C.tbd.CH                                                                        NM     <90                                        I    (none)   (1-cyclo-     NM     <90                                                      hexenyl)C.tbd.CH                                                J    (none)   Bu.sub.3 SnC.tbd.CH                                                                         NM     <90                                        ______________________________________                                         *comparative                                                                  .sup.a Sample A was not irradiated.                                      

As can be seen from the data in Table B, Samples C and D, when comparedto sample A which was not irradiated, showed that irradiation improvedpolymerization rates and yields. Samples C and D, when compared tosample B in which no cocatalyst is used, showed improved polymer yield.Samples F to J showed that the use of various terminal alkynes increasedthe rate of metathesis polymerization of cyclic olefin, compared toSample E.

Examples 5 to 7 illustrate the advantages of using organosilanecocatalyst.

EXAMPLE 5

This example illustrates the effect of organosilane cocatalystcontaining at least one silicon-bonded alkenyl group on catalystactivity and stability.

Procedure 1 was employed, with 10 mg of Ir-2 in 2.0 mL CH₂ Cl₂.Immediately after preparation, 0.25 mL of this catalyst solution wasadded to 20.0 g monomer in CH₂ Cl₂, and gel times (method 1-C) weremeasured. The trial was repeated 10 minutes after preparation of thecatalyst solution and again 2 hours after preparation of the catalystsolution. The above described series of three experiments was repeatedexcept that 28 mg of 1,3-bis(5-hexenyl)tetramethyldisiloxane (cocatalystA) was added to the Ir-2 solution before use. The series was once againrepeated as described except that 43 mg of1,3,5,7-tetravinyltetramethylcyclotetrasiloxane (cocatalyst B) was addedto the Ir-2 solution before use. The data is shown in Table C, below.

                  TABLE C                                                         ______________________________________                                        Gel times (in min) in the presence of organosilane                             ##STR18##                                                                    Cocatalyst                                                                            Immediate   After 10 minutes                                                                           After 2 hours                                ______________________________________                                        none*   3:00        3:30         25:00                                        A       5:00        5:00         7:30                                         B       2:00        2:00         2:00                                         ______________________________________                                         *comparative                                                             

The data in Table C show that each of cocatalysts A and B stabilized thecatalyst in solution. Cocatalyst B was a particularly effectivestabilizer, and also increased catalyst activity, reflected in theshorter gel time, and was preferred in some applications.

EXAMPLE 6

This example illustrates the effect of organosilane cocatalystcontaining at least one ##STR19## group on catalyst solubility.

Approximately 3 mL of CH₂ Cl₂ was required to completely dissolve 3.1 mgof Ir-2. To test improvements in solubility, 20.6 mg Ir-2 was mixed with0.4 mL CH₂ Cl₂, but much material remained undissolved. Upon addition of0.1 mL of 1,3-divinyltetramethyldisiloxane (DVTMDS) to the mixture,almost all Ir-2 compound material dissolved yielding a slightly turbidsolution; the cocatalyst increased the solubility of the transitionmetal compound by a factor of approximately 40. Similar trialsdemonstrated improved solubility of catalysts in the presence of otherorganosilane cocatalysts as shown in Table D, below.

                  TABLE D                                                         ______________________________________                                        Solubility increase in transition                                             metal catalysts with organosilane cocatalyst                                                                Solubility                                      Catalyst Cocatalyst           Increase                                        ______________________________________                                        IR-2     DVTMDS               40                                              Ir-2     1,3,5,7-tetravinyltetramethylcyclo-                                                                20                                                       tetrasiloxane                                                        Ir-2     pentamethyldisiloxane                                                                              30                                              Ir-1     methylphenylsilane   30                                              Ir-1     diethylsilane        ≧10                                      Ir-1     triethylsilane       ≧10                                      ______________________________________                                    

EXAMPLE 7

This example demonstrates that improved polymer yields and improvedcontrol over molecular weight can be provided by organosilanecocatalysts.

Procedure 1 employing CH₂ Cl₂ as solvent was used. The data is shown inTable E, below.

                  TABLE E                                                         ______________________________________                                        Yield and molecular weight control                                            achieved with organosilane cocatalyst                                                                     Polymer.sup.a                                     Sample  Cat      Cocatalyst Yield %                                                                              M.sub.w                                    ______________________________________                                        A.sup.b *                                                                             Ir-1     (none)      6      118 × 10.sup.4                      B       Ir-1     PhMeSiH.sub.2                                                                            100    17.5 × 10.sup.4                      C       Ir-1     Et.sub.2 SiH.sub.2                                                                       100    22.0 × 10.sup.4                      D       Ir-1     Et.sub.3 SiH                                                                              53    8.44 × 10.sup.4                      ______________________________________                                         Notes:                                                                        .sup.a yield at 2 hr reaction time; M.sub.2 is the weight average             molecular weight                                                              .sup.b not entirely homogeneous.                                              *comparative                                                             

As the data in Table E show, higher yields of polymer were obtained inthe presence of organosilane cocatalyst. Molecular weights in thepresence of organosilane cocatalyst were also lower. Formation of highmolecular weight in an uncontrolled manner such as occurred in Sample Ais undesirable because polymer solutions can be too viscous to handle.

Examples 8 to 12 illustrate the advantages of using oxidativecocatalysts.

EXAMPLE 8

This example demonstrates the enhanced rate of polymerization ofring-strained cyclic olefin in the presence of, as oxidative cocatalyst,ferricenium salt.

Following Procedure 1 with CH₂ Cl₂ as solvent, each sample contained 5mg of Ru-1 dissolved in 0.25 ml and 10 mL of monomer solution. Sample Acontained no other additives. Sample B contained, in addition to theabove, 0.5 mL gammabutyrolactone (GBL). Sample C additionally contained3 mg Cp₂ Fe⁺ PF₆ ⁻ dissolved in 0.5 mL GBL (the iron salt is insolublein CH₂ Cl₂ alone). Sample D contained norbornylene solution and 4 mg Cp₂Fe⁺ PF₆ ⁻ dissolved in 0.5 ml GBL, but no Ru-1. Samples were examined bymethod 1-A. The time to form polymer is indicated in Table F. Samples A,B, and D are presented for comparison. The data are shown in Table F,below.

                  TABLE F                                                         ______________________________________                                        Polymerization with Ru catalyst                                               and ferricenium cocatalyst                                                    Sample Catalyst       Time (min) to form Polymer                              ______________________________________                                        A*     Ru-1           15                                                      B*     Ru-1 + GBL     26                                                      C      Ru-1 + Cp.sub.2 Fe.sup.+ PF.sub.6.sup.-                                                       1                                                      D*     Cp.sub.2 Fe.sup.+ PF.sub.6.sup.-                                                             (no polymer at 37 min.)                                 ______________________________________                                         *comparative                                                             

The data in Table F demonstrated that the time to observepoly(norbornylene) in the presence of Ru-1 was shortened by at least anorder of magnitude in the presence of ferricenium salt (Sample C),compared to Sample A or Sample B containing lactone (cyclic ester). Theoxidative cocatalyst ferricenium salt was not, by itself, a catalyst(Sample D).

EXAMPLE 9

This example demonstrates the enhanced rate of polymerization in thepresence of ferricenium salt for a Group 9-containing catalyst.Procedure 1 (and 1B) with CH₂ Cl₂ solvent was used. The data are shownin Table G, below. Samples A and B are presented for comparison.

                  TABLE G                                                         ______________________________________                                        Group 9 catalyst with Cp.sub.2 Fe.sup.+ PF.sub.6.sup.-  cocatalyst            Sample Cp.sub.2 Fe.sup.+ PF.sub.6.sup.- (mg)                                                       GBL (total, ml)                                                                            Time (min)                                  ______________________________________                                        A*     0             0            2                                           B*     0             1.0          9                                           C*     1             1.1          1                                           ______________________________________                                         *Comparative                                                                  Note: Procedure 1 with CH.sub.2 Cl.sub.2 solvent, 1 mg of Ir1 catalyst an     10 mL monomer solution. Polymer was observed by method 1B.               

As the data in Table G show, faster rates of polymerization wereobserved with ferricenium salt oxidative cocatalyst and Ir-1. GBL wasadded to Sample B to provide a convenient rate of reaction and moreaccurate comparison; the addition of GBL slows the rate ofpolymerization.

EXAMPLE 10

This example illustrates that various oxidative salt cocatalysts wereuseful with various transition metal catalysts, as shown in Table H,below.

                  TABLE H                                                         ______________________________________                                        Various catalysts with                                                        various oxidative salt cocatalysts                                            Sam- Oxidative    Cata-   Pro-                                                ple  salt         lyst    cedure                                                                              Time (method)                                 ______________________________________                                        A*   (none)       Ir-1    1.sup.a                                                                             8    (1-B)                                    B    Ph.sub.3 C.sup.+ PF.sub.6.sup.-                                                            Ir-1    1.sup.a                                                                             1    (1-C, viscous)                           C    Ag.sup.+ PF.sub.6.sup.-                                                                    Ir-1    1.sup.a                                                                             1    (1-C, viscous)                           D*   (none)       Ir-1    1.sup.b                                                                             30   (1-A, solids                                                                  filled vial)                             E    Ag.sup.+ PF.sub.6.sup.-                                                                    Ir-1    1.sup.b                                                                             1    (1-A, solids                                                                  filled vial)                             F*   (none)       Ir-2    1.sup.c                                                                             120  (1-C, very                                                                    viscous)                                 G    Ag.sup.+ PF.sub.6.sup.-                                                                    Ir-2    1.sup.c                                                                             <10  (1-C, gel)                               H*   (none)       Ir-2    1.sup.b                                                                             17   (1-A, exotherm)                          I    Na.sup.+ SbF.sub.6.sup.-                                                                   Ir-2    1.sup.b                                                                             9    (1-A, exotherm)                          J    Zn.sup.2+ (BF.sub.4.sup.-).sub.2                                                           Ir-2    1.sup.b                                                                             3    (1-A, exotherm)                               (hydrate)                                                                K    Zn.sup.2+ (acetate.sup.-).sub.2                                                            Ir-2    1.sup.b                                                                             14   (1-A, exotherm)                               (dihydrate)                                                              L    Cu.sup.2+ (BF.sub.4.sup. -).sub.2                                                          Ir-2    1.sup.b                                                                             5    (1-A, exotherm)                               (45% in H.sub.2 O)                                                       M*   (none)       Ru-1    1.sup.b                                                                             16   (1-A, low yield)                         N    Zn.sup.2+ (BF.sub.4.sup.-).sub.2                                                           Ru-1    1.sup.b                                                                             8    (1-A, good                                                                    yield)                                   ______________________________________                                         *comparative                                                                  Notes:                                                                        .sup.a Procedure 1 in CH.sub.2 Cl.sub.2 solvent with 1.0 ml BL, 1 mg Ir1      and 1 mg of the indicated oxidant.                                            .sup.b Procedure 1 in ethyl acetate solution.                                 .sup.c Procedure 2, with 5norbornen-2-yl acetate monomer in ethyl acetate     solution at 60° C.                                                

The data in Table H show faster rates of polyermization for theindicated catalysts (Ir-1, Ir-2, Ru-1) and oxidative salt cocatalysts,as compared to the rates in the absence of cocatalyst. A comparison ofSamples B and C to Sample A (no cocatalyst), a comparison of Sample E toSample D (no cocatalyst), and a comparison of Sample G to Sample F (nococatalyst) shows that use of a cocatalyst greatly increased the speedof polymerization. Note that in E and F an estersubstituted monomer wasused. Similarly, a comparison of Samples I to L to Sample H (nococatalyst), and a comparison of Sample N to Sample M (no cocatalyst)show increased speed of polymerization when a cocatalyst was used. Notethat Samples D to N all contain organic-functional group in the solvent(ethyl acetate).

EXAMPLE 11

This example illustrates the use of oxidative cocatalysts with Group6-containing metal catalysts, also employing the use of photolysis.

Following Procedures 3 and 5, each sample contained W(CO)₆ as catalyst,tris(4-bromophenyl)aminium hexachloroantimonate cocatalyst ("aminium" inTable I, below), and NB at 50% by weight in toluene solvent.

                  TABLE I                                                         ______________________________________                                        Oxidative cocatalysts with                                                    Group 6-containing catalysts                                                  Sample   Method         Cocatalyst                                                                              Yield, %                                    ______________________________________                                        A        3 (60° C., no light)                                                                  aminium   15                                          B        5 (light)      aminium   87                                          ______________________________________                                    

Comparison of samples A and B showed improved yields of polymer obtainedwith oxidative cocatalyst and photolysis.

EXAMPLE 12

This example illustrates the use of oxidative cocatalysts containingoxygen to non-oxygen double bond. Data are presented in Table J, below.

                  TABLE J                                                         ______________________________________                                        Various catalysts with various oxidative                                      cocatalysts containing oxygen to non-oxygen double bond                             Oxidative                      Time                                     Sample                                                                              cocatalyst   Catalyst Procedure                                                                              (method)                                 ______________________________________                                         A*   (none)       Ir-1     1.sup.a  8 (1-B)                                  B      -p-benzoquinone                                                                           Ir-1     1.sup.a  3 (1-B)                                  C     benzophenone Ir-1     1.sup.a  2 (1-B)                                   D*   (none)       Ir-3     1.sup.b  420 (1-B)                                E     Me.sub.3 NO  Ir-3     1.sup.b  4 (1-B)                                  ______________________________________                                         *Comparative                                                                  Notes:                                                                        .sup.a CH.sub.2 Cl.sub.2 solvent with 1.0 ml GBL, 1 mg Ir1 and 1 mg of th     indicated oxidant.                                                            .sup.b 2.0 mg of Ir3 in 12.1 g of NB, 25% in ethanol.                    

The data in Table J show that faster rates of polymerization wereobserved when oxidative cocatalyst-containing oxygen to non-oxygendouble bond was employed. This can be seen in comparison of Samples Band C to Sample A, and comparison of Sample E to Sample D.

Examples 13 and 14 demonstrate the advantages of usingheteroatom-containing alkene cocatalysts.

EXAMPLE 13

This example demonstrates the use heteroatom-containing alkene, and amethod employing photolysis in one step of a two-step process.

Using Procedure 3, a sample containing 0.183 g W(CO)₆, 0.037 g ethylvinyl ether cocatalyst, and 15 ml 1,2-dichloroethane was prepared andirradiated for 20 min, during which time a light yellow color developed.A 3 ml aliquot of the irradiated solution was into a separate vesselcontaining 5 g of degassed norbornadiene under nitrogen and in the dark.Within 15 minutes (in the dark), a highly swollen polynorbornadiene gelwas obtained. Isolated was 0.081 g of solid polymer.

EXAMPLE 14

This example demonstrates the use of heteroatom-containing alkene withGroup 8 and Group 9 transition metal-containing compounds.

Each sample was prepared according to Procedure 1. Polymerization rates,yields and/or molecular weights were measured, and are presented inTable K, below.

                                      TABLE K                                     __________________________________________________________________________    Heteroatom-containing Alkene Cocatalysts                                      Sample                                                                            Catalyst                                                                           Cocatalyst                                                                             Solvent                                                                            Method                                                                             Rate Yield                                                                             M.sub.w × 10.sup.-4                __________________________________________________________________________     A* Ru-1 (none)   CH.sub.2 Cl.sub.2                                                                  1-C  >322 17  44.8.sup.a                               B   Ru-1 pyran.sup.b                                                                            CH.sub.2 Cl.sub.2                                                                  1-C  240  56  25.2.sup.a                                C* Ru-1 (none)   CH.sub.2 Cl.sub.2                                                                  1-B  15                                                D   Ru-1 furan    CH.sub.2 Cl.sub.2                                                                  1-B  10                                                E   Ru-1 pyran.sup.c                                                                            CH.sub.2 Cl.sub.2                                                                  1-B   5                                                F   Ru-1 2,5-dihydrofuran                                                                       CH.sub.2 Cl.sub.2                                                                  1-B  10                                                G   Ru-1 3-tmscp.sup.d                                                                          CH.sub.2 Cl.sub.2                                                                  1-B   5                                                __________________________________________________________________________     Notes:                                                                        .sup.a weight average molecular weight.                                       .sup.b 0.2 g 3,4dihydro-2-H-pyran per 30 mg Ru1.                              .sup.c 0.1 g 3,4dihydro-2-H-pyran per 30 mg Ru1.                              .sup.d 0.1 g 3trimethylsilylcyclopentene per 30 mg Ru1.                  

A comparison of samples A and B in Table K shows that the use ofheteroatom-containing alkene cocatalyst provided faster rates ofpolymerization, higher polymer yields, and better control over molecularweight of the polymer obtained. Comparison of samples D-G to sample Cshows that faster polymerization rates were achieved withheteroatom-containing alkenes.

Examples 15 to 17 illustrate the advantages of methods employingphotolysis.

EXAMPLE 15

This example demonstrated the method employing photolysis for apolymerizable composition containing a one-part catalyst (nococatalyst), and no solvent. The sample contained 0.020 g W(CO)₆ and5.00 g NB, melted to dissolve the catalyst, and purged with nitrogen ina vial which was then sealed. The sample was irradiated for 30 min at50° C. (in the melt), and then kept at 50° C. without irradiation for anadditional 16 hours. The thick, viscous liquid in the vial was submittedfor ¹ H and ¹³ C NMR Nuclear Magnetic Resonance spectroscopy), whichshowed it to be predominately the cis form of polynorbornadiene (bycomparison to published spectra of K. J. Ivin, D. T. Laverty and J. J.Rooney, Makromol. Chem. 1977, 178, 1545-1560 . An identical sample, keptat 50° C. for 16 hours without irradiation, showed only norbornylene by¹ H and ¹³ C NMR.

This example demonstrates that a polymerizable composition containingone-part catalyst and cyclic olefin can be caused to polymerize by amethod employing photolysis. It is particularly advantageous that, inthis example, polymerization does not occur in the absence ofphotolysis, that is, it is possible to prevent polymerization of apolymerizable composition until a desired time, and then to initiate ortrigger the polymerization by photolysis.

EXAMPLE 16

The example demonstrates the use of various one-part and two-partcatalysts containing Group 6 transition metal compounds, which showedgreater activity when photolysis was employed. The data is shown inTable L below for one-part catalysts. The data for two-part catalystswas presented in Tables B and I, above.

                  TABLE L                                                         ______________________________________                                        Sam-                       Cocata-       Yield,                               ple  Catalyst     Solvent  lyst   Method %                                    ______________________________________                                        A*   W(CO).sub.6  CH.sub.2 Cl.sub.2                                                                      (none) 3      0                                    B*   W(CO).sub.6  toluene  (none) 5      50                                   C*   W(CO).sub.6  CH.sub.2 Cl.sub.2                                                                      (none) 5      74                                   D*   Mo(CO).sub.4 (NBD)                                                                         CH.sub.2 Cl.sub.2                                                                      (none) 3      a                                    E*   Mo(CO).sub.4 (NBD)                                                                         CH.sub.2 Cl.sub.2                                                                      (none) 5      a                                    F*   Mo(CO).sub.6 CH.sub.2 Cl.sub.2                                                                      (none) 5      50                                   G*   (mesitylene)-                                                                              CH.sub.2 Cl.sub.2                                                                      (none) 5      a                                         W(CO).sub.3                                                              ______________________________________                                         *comparative                                                                  .sup.a Not measured, but sufficient yield to provide material for             spectroscopic analysis, ≧5%.                                      

The data in Table L show that polymer yields were higher when photolysiswas employed with a one-part catalyst (Sample B compared to A).

The data in Table B above (Sample D compared to A) show increasedpolymer yields and rates upon photolysis in the presence of terminalalkyne cocatalyst. In Table I, above, Sample B (irradiated) gave ahigher polymer yield than Sample A (dark) in the presence of oxidativesalt cocatalyst.

EXAMPLE 17

This example demonstrates the use of various one-part catalystscontaining Group 7 and Group 8 transition metal-containing compounds.Samples were prepared and times to form polymer measured, with resultsshown in Table M, below.

                  TABLE M                                                         ______________________________________                                        One-part Group 8 and Group 9 catalysts                                                                           Time to form                               Sample                                                                              Catalyst  Solvent    Method  polymer (min)                              ______________________________________                                        A     Ru-2      EtOH/H.sub.2 O                                                                           1-A (dark)                                                                            120                                        B     Ru-2      EtOH/H.sub.2 O                                                                           4-A (light)                                                                           5                                           C*   RuCl.sub.3                                                                              EtOH/H.sub.2 O                                                                           1-A (dark)                                                                            120                                              (hydrate)                                                                D*   Ru-1      EtOH       1-A (dark)                                                                            60                                         E     Ru-1      EtOH       4-A (light)                                                                           7                                           F*   Ru-1      CH.sub.2 Cl.sub.2                                                                        1-B (dark)                                                                            9                                          G     Ru-1      CH.sub.2 Cl.sub.2                                                                        4-B (light)                                                                           6                                           H*   Re.sub.2 (CO).sub.10                                                                    CH.sub.2 Cl.sub.2                                                                        1-A (dark)                                                                            >60                                        I     Re.sub.2 (CO).sub.10                                                                    CH.sub.2 Cl.sub.2                                                                        4-A (light)                                                                           30                                         ______________________________________                                         *comparative                                                             

In Table M, a comparison of samples A and B (which are the same exceptthat B was irradiated as were samples E, G and I), of D and E, of F andG, and of H and I, shows that rates of polymerization were faster whensamples were irradiated. Sample C using commercial RuCl₃.xH₂ O ispresented for purposes of comparison to the background art; greateramounts of precipitate were formed in sample C than in sample A in 2 hr,that is, Ru-2 is slower than RuC₁₃ unless irradiated (sample B). In someprocesses, large differences between dark and irradiated rates may bepreferred.

EXAMPLE 18

This example demonstrates the formation of a self-supporting sheet-likearticle using polymerizable compositions of the present invention.

Twenty-one mg of Ir-1 was placed in 4.6 g CH₂ Cl₂. Et₂ SiH₂ (39 mg) wasadded, and the Ir compound dissolved. 5.51 g of dicyclopentadiene (whichhad been stored over alumina for approximately 16 hr to remove coloredimpurities) was added. A portion of this sample was poured into a pan toproduce a liquid film of less tha 1 mm thickness. The pan was thenheated to 100° C. Within 5 min, a solid had formed, and was peeled fromthe pan to produce a self-supporting sheet. The sheet was sufficientlyflexible and tough that it could be handled and manipulated withoutparticular care, that is, it was not fragile nor very brittle.

Various modifications and alterations of this invention will becomeapparent to those skilled in the art without departing from the scopeand spirit of this invention, and it should be understood that thisinvention is not to be unduly limited to the illustrative embodimentsset forth herein.

We claim:
 1. A polymerizable composition comprisinga) at least onering-strained non-conjugated cyclic olefin, and b) a two-part transitionmetal containing catalyst which is air and moisture stable, whichconsists of(1) at least one transition metal-containing catalystprovided that the oxidation state of the transition metal is in therange of +3 to 0, (2) a cocatalyst selected from the group consisting ofoxidative salts and oxidative compounds containing an oxygen tonon-oxygen double bond.
 2. The composition according to claim 1, whereinsaid transition metal in said transition-metal containing catalyst isselected from the class consisting of Periodic Group 6, 8, and 9 metals.3. The composition according to claim 2 wherein said transition metal isselected from the group consisting of W, Ru, and Ir.
 4. The compositionaccording to claim 1 wherein said cyclic olefin is norbornene orsubstituted norbornene.
 5. The composition according to claim 1 whereinsaid two-part catalyst contains said oxidative compound as cocatalyst.6. The composition according to claim 1 wherein said two-part catalystcontains said oxidative salt as cocatalyst.
 7. The composition accordingto claim 6 wherein said oxidative cocatalyst is selected from the groupconsisting of Ag⁺ PF₆ ⁻, (eta⁵ -cyclopentadienyl)₂ Fe⁺ PF₆ ⁻,tris(4-bromophenyl)aminium⁺ SbF₆ ⁻, Ph₃ C⁺ PF₆ ⁻, Zn²⁺ (BF₄ ⁻)₂, Zn²⁺(acetate⁻)₂, and Cu²⁺ (BF₄ ⁻)₂.
 8. A method for polymerizingring-strained cyclic olefins comprising the steps of:a) providing thecomposition as disclosed in claim 1, and b) allowing said composition topolymerize.
 9. The method according to claim 8 wherein saidpolymerization step takes place in the presence of at least one of heatand actinic radiation.
 10. The polymerized composition according toclaim
 1. 11. A self-supported sheet-like article comprising thepolymerized composition according to claim
 10. 12. A molded articlecomprising the polymerized composition according to claim
 10. 13. Acoated article comprising the composition according to claim 10.